Acrylates containing an alcohol, aldehyde and/or ether functional group, process for their manufacture and their application to the production of new polymers and copolymers

ABSTRACT

Process for the preparation of the acrylates chosen from those of formula ##STR1## those of formula ##STR2## and those of the formula ##STR3## useful in the production of new polymers and copolymers.

This application is a divisional of application Ser. No. 08/022,226,filed Feb. 25, 1993, now U.S. Pat. No. 5,332,836, which is a divisionalof application Ser. No. 07/721,751, filed Jun. 27, 1991, now U.S. Pat.No. 5,206,389, issued Apr. 27, 1993.

BACKGROUND OF THE INVENTION

The present invention relates to new acrylates carrying at least twofunctional groups chosen from the alcohol, aldehyde and ether functionalgroups, to a process for their manufacture and to the production of newpolymers and copolymers from the said acrylates.

U.S. Pat. No. 3,743,669 discloses a process for the preparation ofacrylic compounds of formula ##STR4## by reaction in a liquid phase at atemperature approximately from 0° to 200° C. of an α,β-olefinicallyunsaturated carboxylic acid derivative of formula CH₂ ═CHY with analdehyde of formula RCHO, Y being chosen from ##STR5## each of R¹ to R⁴denoting an alkyl (C₁ -C₁₂), cycloalkyl (C₅ -C₁₂), aryl, aralkyl oralkaryl, and R denoting alkyl (C₁ -C₈), alk-(C₁ -C₄)aryl, aralkyl (C₁-C₄) or aryl, the said reaction being carried out in the presence of acatalytic quantity of a cyclic tertiary amine containing at least onenitrogen atom common to three rings. This reaction is very s low at roomtemperature. Thus, the reaction of 7.9 moles of acetaldehyde and 5.27moles of ethyl acrylate at room temperature in the presence of 0.26moles of diazabicyclo[2,2,2]-octane produces 93% of ethyl2-(1-hydroxyethyl)acrylate only after 7 days. The same reaction carriedout at 120°-124° C. takes place with a conversion of 82% at the end of 8hours, but at the expense of selectivity. Furthermore, the AssigneeCompany has found that this reaction does not occur, even after 10 days,with some aldehydes whose carbonyl group is sterically hindered, such astrimethylacetaldehyde.

Bearing in mind the special behaviour which may be expected of acrylatescontaining a hydroxyl group in their structure, the Assignee Company hasbeen concerned with obtaining new acrylates by functionalisation bymeans of dialdehydes.

SUMMARY OF THE INVENTION

A first subject of the present invention consists, therefore, of newacrylates chosen from those of formula ##STR6## those of formula##STR7## those of formula ##STR8## in which: R is a radical chosen fromalkyl radicals containing from 1 to 12 carbon atoms, cycloalkyl radicalscontaining from 5 to 12 carbon atoms, and aryl, arylalkyl and alkylarylradicals,

Y is a radical chosen from alkylene radicals containing from 1 to 12carbon atoms, arylene radicals containing from 6 to 12 carbon atoms,heterocyclic radicals whose ring contains from 5 to 12 members and whoseheteroatom is chosen from nitrogen, oxygen and sulphur, and alkylaryleneradicals in which the alkyl part contains from 1 to 4 carbon atoms, andY not being able to denote 1,4-phenylene when R denotes methyl,

Z is a hydrocarbon radical containing at least two carbon atoms formingwith the oxygen and the two adjacent carbons a ring containing from 4 to8 members and preferably containing 5 or 6 members.

As examples of radicals R there may be mentioned especially the methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, phenyl and benzylradicals. As examples of radicals Y there may be mentioned the radicals(CH₂)_(n) in which n is an integer ranging from 4 to 12, phenylene(ortho, meta, para) radicals C₆ H₄, 3,3'-diphenyl and 4,4'-diphenylradicals, the 2,5-thiophenyl radical and the 2,5-furyl radical.

As examples of radicals Z there may be mentioned especially the radicals(CH₂)₂ and (CH₂)₃ and the phenylene radical C₆ H₄.

A second subject of the present invention consists of a process for thepreparation of the acrylates of formulae (I) to (III). Although a commonfeature of the preparation of all these compounds is a stage involvingan acrylate derived from an alcohol ROH and a dialdehyde, theirsynthesis nevertheless exhibits special features, depending on whethermonoacrylates of formulae (I) and (III) or else diacrylates of formula(II) are involved. This is why the process of preparation according tothe invention will now be described with reference to each of theclasses of compounds according to the invention.

The preparation of the acrylates of formula (I) to (III) is carried outby reacting an acrylate of formula: ##STR9## in which R is defined asabove with a dialdehyde of formula ##STR10## in which Y is defined asabove, in the presence of an effective quantity of at least onefunctionalisation catalyst. As a functionalisation catalyst which issuitable for the reaction with an aldehyde there may be mentionedespecially relatively strong bases such as cyclic tertiary aminescontaining at least one nitrogen atom common to three rings, describedin U.S. Pat. No. 3,743,669, for example diazabicyclo[2,2,2]octane,quinuclidine and α-quinuclidinol. An effective quantity offunctionalisation catalyst obviously depends on the nature of thelatter, but also on the acrylate of formula (IV) and the aldehyde offormula (V). It is generally approximately between 2 and 20%, preferablyapproximately between 4 and 10 mol % relative to the sum of thereactants present--acrylate and dialdehyde.

As an example of dialdehydes of formula (V) there may be mentionedespecially terephthalaldehyde, isophthalaldehyde, orthophthalaldehyde,glutaraldehyde, hexanedial, decanedial, dodecanedial,thiophene-2,5-dicarboxyaldehyde, furan-2,5-dicarboxaldehyde,3,3'-biformyldiphenyl and 4,4'-biformyldiphenyl.

The process of preparation according to the invention can beadditionally carried out in the presence of at least one electrophilicactivator such as lithium chloride or fluoride in a quantity which maybe up to approximately 5 mol % relative to the sum of the reactantspresent--acrylate and dialdehyde.

The process according to the invention may be additionally carried outin the presence of an organic solvent such as tetrahydrofuran, methylenechloride, chloroform, dioxane, acetonitrile, methyl ethyl ketone,ethanol, ethyl acetate and the like.

To make use of the process according to the invention a temperature ofbetween 15° C. and 125° C. may be chosen, preferably approximatelybetween 20° C. and 50° C., and not exceeding the boiling temperature ofthe solvent when a solvent is employed.

The reactants may be present in the reaction medium in anyconcentration. However, for reasons of kinetics it is generallypreferable to avoid an excessively high dilution with the solvent and toconform to an acrylate/dialdehyde molar ratio of approximately between0.2 and 10. The possible excess of one of the two reactants in relationto the other enables it then to act as a solvent.

Finally, the reaction according to the invention may be carried out inthe presence of an effective quantity of at least one polymerisationinhibitor. As examples of polymerisation inhibitors which can beemployed there may be mentioned especially phenothiazine, hydroquinonemethyl ether, N,N-diethylhydroxylamine, nitrobenzene,di-tert-butylcatechol, hydroquinone, p-anilinophenol,di(2-ethylhexyl)octylphenyl phosphite,2,5-di-tert-butyl-4-hydroxytoluene, methylene blue and their mixtures inall proportions. An effective quantity of polymerisation inhibitor isgenerally between 0.05% and 0.5% by weight of acrylic compound.

Although atmospheric pressure is generally satisfactory, the processaccording to the invention can also be used under pressure.

Depending on whether it is desired to direct the reaction according tothe invention towards the production of monoacrylates of formulae (I)and (III) or else towards the production of diacrylates of formula (II),some special conditions must, nevertheless, be obeyed. In fact, thereaction according to the invention generally produces a mixture of amonoacrylate and of a diacrylate which must then, at a time chosen forstopping the reaction, be separated by a conventional separationtechnique. In some cases, the separation is facilitated by thedifference in physical state between the two compounds formed, at normalpressure and temperature. Thus, for example, in the case ofterephthalaldehyde, the monoacrylate formed is a liquid, whereas thediacrylate formed is a white solid. As already mentioned elsewhere, themonoacrylates of formula (III) are formed in preference to themonoacrylates of formula (I) when the dialdehyde of formula (V) which isemployed for the reaction according to the invention is of a structuresuch that a cyclisation incorporating one of the oxygen atoms of thedialdehyde can easily take place. Such a possibility is particularlyfavourable when Y is a (CH₂)₂ or (CH₂)₃ radical or else a phenyleneradical C₆ H₄ on which the aldehyde functional groups are situated inthe ortho position.

The composition of the mixture of monoacrylate and diacrylate which isformed by the reaction according to the invention is affected in acomplex manner by a set of parameters such as:

the reaction time, it being possible for the latter to range fromapproximately 1 hour to approximately 12 days, depending on the reactiontemperature and pressure which are chosen; the monoacrylate is generallyformed first, in a virtually quantitative manner, after a relativelyshort time, of the order of a few hours at room temperature; in a secondstage the monoacrylate disappears progressively, to form the diacrylate;

the nature of the solvent employed: all conditions being otherwiseequal, the diacrylate is formed much more easily in tetrahydrofuran ormethylene chloride than in chloroform;

the quantity of solvent employed: dilution with a solvent such astetrahydrofuran slows down the first stage of formation of themonoacrylate and, to a still much greater extent, the second stage offormation of the diacrylate;

the quantity of functionalisation catalyst employed: all conditionsbeing otherwise equal, an increase in the quantity of catalyst resultsin a slight acceleration of the monoacrylate formation stage and in amore pronounced acceleration of the diacrylate formation stage;

the acrylate/dialdehyde molar ratio: in the presence of solvent and atconstant total volume, that is to say apart from the dilution effect, anincrease in this ratio produces the acceleration of the diacrylateformation;

the reaction temperature: all conditions being otherwise equal, anincrease in the temperature is reflected in a faster formation of thediacrylate.

The new acrylates according to the invention can polymerise orcopolymerise with other ethylenically unsaturated monomers such asethylene, as well as:

an alkyl acrylate or methacrylate in which the linear or branched alkylgroup, optionally substituted, for example, with at least one halogenatom such as chlorine or fluorine and/or by at least one hydroxyl group,contains from 1 to 20 carbon atoms,

an aryl acrylate or methacrylate such as benzyl methacrylate,

a vinylaromatic hydrocarbon such as styrene, vinyltoluene,α-methylstyrene, 4-methylstyrene, 3-methylstyrene, 4-methoxystyrene,2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene,3,4-dimethylstyrene, 2-chlorostyrene, 3-chlorostyrene,4-chloro-3-methylstyrene, 3-tert-butylstyrene, 2,4-dichlorostyrene,2,6-dichlorostyrene and 1-vinylnaphthalene;

an unsaturated nitrile such as acrylonitrile or methacrylonitrile,

an N-substituted maleimide such as N-ethylmaleimide,N-isopropylmaleimide, N-n-butylmaleimide, N-isobutylmaleimide,N-tert-butylmaleimide, N-n-octylmaleimide, N-cyclohexylmaleimide,N-benzylmaleimide and N-phenylmaleimide,

an unsaturated dicarboxylic acid anhydride such as maleic anhydride,itaconic anhydride, citraconic anhydride or tetrahydrophthalicanhydride,

acrylic or methacrylic acid,

a polyol acrylate or methacrylate such as the diacrylates anddimethacrylates of ethylene glycol, propylene glycol, 1,3-butanediol,1,4-butanediol, 1,6-hexanediol, neopentylglycol, 1,4-cyclohexanediol,1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol,2-ethyl-2-methyl-l,3-propanediol, 2,2-diethyl-l,3-propanediol,diethylene glycol, dipropylene glycol, triethylene glycol, tripropyleneglycol, tetraethylene glycol, tetrapropylene glycol, trimethylolethane,trimethylolpropane, glycerol, pentaerythritol, the triacrylates andtrimethacrylates of trimethylolethane, trimethylolpropane, glycerol andpentaerythritol, pentaerythritol tetraacrylates and tetramethacrylates,dipentaerythritol di(meth)acrylates to hexa(meth)acrylates,poly(meth)acrylates of mono- or polyethoxylated or mono- orpolypropoxylated polyols such as triethoxylated trimethylolpropane andtripropoxylated trimethylolpropane triacrylate and trimethacrylate;tripropoxylated glycerol triacrylate and trimethacrylate; andtetraethoxylated pentaerythritol triacrylate, trimethacrylate,tetraacrylate and tetramethacrylate,

an epoxidised acrylate or methacrylate chosen from2-epoxyethylbicyclo[2.2.1]hept-5(6)-yl (meth)acrylate,epoxydicyclopentyloxyethyl acrylate, and those of formula: ##STR11## inwhich R₁ is chosen from the hydrogen atom and the methyl radical, and nis an integer ranging from 1 to 16,

those of formula: ##STR12## in which R₁ is chosen from the hydrogen atomand the methyl radical, and R₂ is chosen from alkyl radicals containingfrom 1 to 12 carbon atoms and aryl radicals containing from 6 to 12carbon atoms,

and those of formulae: ##STR13## in which R₁ is chosen from the hydrogenatom and the methyl radical, an acrylamide or methacrylamide or adialkylaminoalkyl acrylate or methacrylate, and their quaternary salts,

2-(2-norbornyloxy)ethyl and 2-(2-dimethanodecahydronaphthyloxy)ethylacrylate and methacrylate, and

acrylic and methacrylic oxazolidones chosen from those of formula:##STR14## in which formulae: R¹ is chosen from the hydrogen atom and themethyl radical,

n is an integer ranging from 1 to 12,

m is an integer ranging from 1 to 3, and

R² is a branched or cyclic linear alkyl or aromatic hydrocarbon radicalcontaining from 5 to 12 carbon atoms,

it being possible for the said oxazolidones to be obtained by reaction,between 30° C. and 90° C., of a compound carrying a (meth)acrylicfunctional group with a compound carrying at least one isocyanatefunctional group,

acrylic and methacrylic compounds chosen from those of formula:##STR15## in which: R¹ is chosen from the hydrogen atom and the methylradical,

A is chosen from the radicals (CH₂)_(n) in which n is an integer from 2to 12 and the radical --(CH₂ CH₂ O)_(d) --CH₂ CH₂ --, d being an integerranging from 1 to 20,

X is chosen from sulphur and oxygen atoms,

Y is chosen from sulphur and oxygen atoms,

with the condition that X is a sulphur atom and Y is an oxygen atom whenA is the radical --(CH₂ CH₂ O)_(d) --CH₂ CH₂ --, and

R is chosen from alkyl radicals containing from 1 to 20 carbon atoms and--(CH₂)_(p) SR.sup. 3 groups in which p is an integer ranging from 3 to12 and R³ is an alkyl radical containing from 1 to 20 carbon atoms,

those of formula: ##STR16## in which: R¹ is chosen from the hydrogenatom and the methyl radical,

A is chosen from the radicals (CH₂)_(n) in which n is an integer from 2to 12 and the radical --(CH₂ CH₂ O)_(d) --CH₂ CH₂ --, d being an integerranging from 1 to 20, and

X is chosen from sulphur and oxygen atoms,

and those of formula: ##STR17## in which: R¹ is chosen from the hydrogenatom and the methyl radical,

A is chosen from the radicals (CH₂)_(n) in which n is an integer from 2to 12,

m is an integer from 1 to 3, and

Z is chosen from the hydrogen atom, the radicals R² QH, R² being analkyl radical containing from 2 to 12 carbon atoms and Q being chosenfrom oxygen and sulphur atoms and the atoms of metals of groups IA, IIA,IIIA, IB, IIB, VIB, VIIB and VIII of the Periodic Classification,

with the condition that Z is chosen from the hydrogen atom and theradicals R² OH when m=1 and that m is the valency of Z when Z is ametal. Such compounds can be prepared by reaction of an acrylic ormethacrylic compound of formula: ##STR18## in which R¹ A and Y have thesame meanings as in the formula (I), with a pentavalent phosphoruscompound, it being possible for the latter to be, for example, acompound of formula PXT₃ in which X has the same meaning as in formula(II) and T denotes a halogen atom, or else a phosphorus compound offormula: ##STR19## in which R and X have the same meanings as in formula(I) and T denotes a halogen atom or else the pentasulphide P₂ S₅,

and generally any ethylenically unsaturated monomers capable of beingcopolymerised by a radical process under the effect of a free-radicalgenerator such as microwaves, beta, gamma or ultraviolet radiation or achemical initiator such as persulphate, peroxide, hydroperoxide or diazocompound.

Thus, a third subject of the present invention consists of a polymercomprising in its chain at least one unit derived from an acrylate offormula (I), (II) or (III) with the condition that Y may also denote1,4-phenylene when R denotes methyl and, if appropriate, at least oneunit derived from another ethylenically unsaturated monomer such asdescribed above. In the case of copolymers, the polymerisationconditions will be chosen to be as close as possible to those usuallyemployed for the polymerisation of the ethylenically unsaturatedmonomer, namely, for example:

a temperature of 140° C. to 300° C. and a pressure approximately from1000 to 3000 bars when this comonomer is ethylene,

a temperature approximately from 30° C. to 90° C. when this comonomer isan acrylic or methacrylic compound,

a temperature approximately from 80° C. to 200° C. when this comonomeris a vinylaromatic hydrocarbon.

The polymers of this invention can be used in the same conventionalmanner as other acrylic and methacrylic polymers, e.g., formed intomolded, cast, and extruded articles, coating materials, etc.

(In the above description and throughout the specification and claims,the numerical range of "from x to y", x and y being integers, isintended to include both x and y.)

The entire disclosure of all applications, patents, and publications,cited above and below, and of corresponding French Application 90 08108,filed Jun. 27, 1990, are hereby incorporated by reference.

The following examples are given by way of illustration of the presentinvention, no limitation being employed.

Examples 1 to 25

26.8 g (0.2 mol) of terephthalaldehyde, x mol ofdiazabicyclo[2.2.2]octane, y mol of methyl acrylate and z ml of solventare introduced successively into a glass round bottom flask of 3 lcapacity fitted with a condenser. The mixture is stirred at thetemperature T (expressed in degrees Celsius) for the period t (expressedin hours). The percentages M of monoacrylate and D of diacrylate whichare present in the reaction mixture at the end of the time t ordetermined by gas phase chromatography and reported in Table I below atthe same time as the reaction parameters. 200 ml of methyl chloride and120 ml of 1 N hydrochloric acid are then added to the mixture. Theaqueous phase is extracted once with 40 ml of methylene chloride. Theorganic phase is washed twice with 80 ml of water and is then dried overmagnesium sulphate. After evaporation of the solvent the mono- ordiacrylate formed is purified on a silica column, the eluent being amixture containing 35% of ethyl acetate and 65 % of petroleum ether. Themonoacrylate (methyl3-(4-carboxaldehydephenyl)-3-hydroxy-2-methylenepropanoate) is acolourless liquid and can be isolated in a 94% yield, for example intest 10. The diacrylate (1,4-di(methyl3-hydroxy-2-methylenecarboxylate)benzene) is a white solid and can beisolated in a 90% yield, for example in test 21. Both were identified bythe following techniques:

proton nuclear magnetic resonance employing a JEOL PMX 60SIspectrometer: the spectra obtained include chemical shifts at:

a) 9.8 (s,1H) 7.3-7.8 (m,4H) 6.2 (m, 1H) 5.9 (m, 1H) 5.5 (m, 1H) 3.9 (m,1H,OH) 3.6 (s,3H) in ppm in the case of the monoacrylate.

b) 7.3 (s,4H) 6.3 (m,2H) 5.8 (m,2H) 5.5 (m,2H) 3.7 (s,6H) 2.9 (m,2H,OH)in ppm in the case of the diacrylate;

infrared spectrophotometry employing a Perkin Elmer 841 spectrometer:the spectra obtained include characteristic bands at:

c) 3477, 1724, 1703, 1631, 1609, 1579, 1439 cm⁻¹ in the case of themonoacrylate,

d) 3459, 1724, 1631 and 1439 cm⁻¹ in the case of the diacrylate;

carbon-13 nuclear magnetic spectroscopy: chemical shifts at 191.9 ppm,165.9 ppm, 148.3 ppm, 141.3 ppm, 135.2 ppm, 129.4 ppm, 127.0 ppm, 126.0ppm, 71.8 ppm and 51.6 ppm in the case of the monoacrylate; at 166.7ppm, 141.8 ppm, 140.3 ppm, 127.1 ppm, 127.0 ppm, 126.2 ppm, 73.0 ppm and52.0 ppm in the case of the diacrylate.

                  TABLE I                                                         ______________________________________                                        Example                                                                              x       y     z     Solvent T   t     M   D                            ______________________________________                                         1     0.1     1.0   50    THF     20  8     98   2                            2     0.1     1.0   50    THF     20  96    46  54                            3     0.1     1.0   50    THF     20  192   35  65                            4     0.1     1.0   50    THF     20  288   19  81                            5     0.1     1.0   50    CH.sub.2 Cl.sub.2                                                                     20  8     95   5                            6     0.1     1.0   50    CH.sub.2 Cl.sub.2                                                                     20  96    35  65                            7     0.1     1.0   50    CH.sub.2 Cl.sub.2                                                                     20  192   26  74                            8     0.1     1.0   50    CH.sub.2 Cl.sub.2                                                                     20  240   23  77                            9     0.1     1.0   50    CHCl.sub.3                                                                            20  96    97   3                           10     0.1     0.4    0    --      20  2.5   96   4                           11     0.1     0.4   10    THF     20  3     94   2                           12     0.1     0.4   44    THF     20  3     94   3                           13     0.1     0.4   44    THF     20  24    82  18                           14     0.1     0.4    4    THF     20  96    50  50                           15     0.1     0.4   164   THF     20  96    98   2                           16     0.4     2.0   20    THF     20  96    30  70                           17     0.4     2.0   20    THF     20  240    9  91                           18     0.1     0.2   50    THF     20  8     80   0                           19     0.1     0.2   50    THF     20  24    96   2                           20     0.1     1.0    0    --      20  2     85   4                           21     0.2     2.0    0    --      20  96     2  96                           22     0.4     2.0   20    THF     45  72    19  81                           23     0.4     2.0   20    THF     45  192    4  96                           24     0.4     2.0   20    THF     55  24    61  39                           25     0.4     2.0   20    THF     55  72    18  82                            26*   0.1     1.0    0    --      20  0.8   95   5                           ______________________________________                                         *test carried out in the presence of lithium chloride.                        THF = tetrahydrofuran.                                                   

Example 26

The experimental procedure of Example 20 is reproduced with thefollowing two exceptions:

0.8 g (0.02 mol) of lithium chloride is added to the reaction mixture,

the reaction is interrupted after 50 minutes.

Analysis of the mixture at the end of the reaction makes it possible todetermine the percentages M of monoacrylate and D of diacrylate whichare shown in the table.

Examples 27 to 35

26.8 g (0.2 mol) of isophthalaldehyde, x mol ofdiazabicyclo[2.2.2]octane, y mol of methyl acrylate, z ml of solventand, if appropriate, q mol of lithium chloride are introducedsuccessively into a glass round bottom flask of 3 l capacity. Themixture is stirred at a temperature of 25° C. for the period t,expressed in hours. The mixture is then treated as in Examples 1 to 25.The percentages M of monoacrylate and D of diacrylate which are presentin the reaction mixture at the end of the time t are determined by gaschromatography and reported in Table II below at the same time as thereaction parameters. The monoacrylate (methyl3-(3-carboxaldehydephenyl)-3-hydroxy-2-methylenepropanoate) and thediacrylate (1,3-di(methyl 3-hydroxy-2-methylenecarboxylate)benzene) arecolourless liquids. They can be isolated in tests 28 and 36 in yields of88% and 96% respectively. Both were identified by the same techniques asthose mentioned in Examples 1 to 25 and exhibit the following spectralcharacteristics:

proton nuclear magnetic resonance:

a) 9.7 (s,1H) 7.3-7.8 (m,4H) 6.2 (m, 1H) 5.8 (m, 1H) 5.5 (m, 1H) 4.0 (m,1H,OH) 3.6 (s,3H) in ppm in the case of the monoacrylate;

b) 7.3 (m,4H) 6.3 (m,2H) 5.8 (m,2H) 5.5 (m,2H) 3.7 (s, 6H) 3.3 (m,2H,OH) in ppm in the case of the diacrylate;

infrared spectrophotometry:

c) absorption bands at 3471 cm⁻¹ 1723 cm⁻¹ 1701 cm⁻¹, 1630 cm⁻¹, 1603cm⁻¹, 1587 cm⁻¹ and 1441 cm⁻¹ in the case of the monoacrylate;

d) absorption bands at 3458 cm⁻¹, 1723 cm⁻¹ 1632 cm⁻¹ and 1441 cm⁻¹ inthe case of the diacrylate;

carbon-13 nuclear magnetic spectroscopy: chemical shifts at 192.1 ppm,165.3 ppm, 142.6 ppm, 141.4 ppm, 135.8 ppm, 132.6 ppm, 128.5 ppm, 128.4ppm, 127.7 ppm, 125.6 ppm, 71.3 ppm and 51.4 ppm in the case of themonoacrylate (FIG. 1c); at 166.1 ppm, 141.8 ppm, 141.2 ppm, 127.8 ppm,125.75 ppm, 125.2 ppm, 124.9 ppm, 71.6 ppm and 51.3 ppm in the case ofthe diacrylate.

                  TABLE II                                                        ______________________________________                                        Example x     y     z    q    Solvent                                                                              t     M   D                              ______________________________________                                        27      0.1   1.0   0    0    --      3    68   1                             28      0.1   1.0   0    0    --      5    85  10                             29      0.1   1.0   0    0    --     24    30  70                             30      0.1   1.0   0    0.02 --      2    82  18                             31      0.1   1.0   0    0.02 --     24    14  86                             32      0.1   1.0   0    0.02 --     48     8  92                             33      0.2   0.4   50   0    THF     3    37   0                             34      0.2   0.4   50   0    THF    12    86   3                             35      0.2   0.4   50   0.02 THF     3    90   3                             36      0.2   2.0   0    0    --     72     2  96                             ______________________________________                                    

Example 37

26.8 g (0.2 mol) of ortho-phthalaldehyde, 11.2 g (0.1 mol) ofdiazabicyclo[2.2.2]octane, 90 ml (1 mol) of methyl acrylate and 50 ml oftetrahydrofuran are introduced successively into a glass round bottomflask of 3 l capacity. The mixture is stirred at 25° C. for 4 hours andis then treated as in Examples 1 to 25. Analysis by gas phasechromatography shows the formation, in an isolated yield of 86%, of acompound identified as that of formula ##STR20## by infraredspectrophotometry by means of a Perkin-Elmer spectrometer. The spectrumobtained includes characteristic bands at 3459 cm⁻¹, 1721 cm⁻¹, 1631cm⁻¹, 1463 cm⁻¹ and 1439 cm⁻¹.

Example 38

0.2 mol of 50% aqueous glutaraldehyde, 1 mol of methyl acrylate, 0.1 molof diazabicyclo[2.2.2 ]octane and 50 ml of dichloromethane areintroduced successively into a glass round bottom flask 3 l in capacity.The mixture is stirred at 25° C. for 144 hours and is then treated as inExamples 1 to 25. Analysis by gas phase chromatography shows theformation, in a 30% yield, of a compound identified as that of formula##STR21## by infrared spectrophotometry by means of a Perkin-Elmer 841spectrometer. The spectrum obtained includes characteristic bands at3435, 1721 and 1632 cm¹ ;

by carbon-13 nuclear magnetic resonance: chemical shifts at 166.0 ppm,165.9 ppm, 141.5 ppm, 140.5 ppm, 124.4 ppm, 124.0 ppm, 96.3 ppm, 91.5ppm, 73.1 ppm, 65.9 ppm, 51.3 ppm, 31.7 ppm, 31.1 ppm, 30.4 ppm, 29.2ppm, 21.8 ppm, 17.1 ppm and 15.6 ppm;

by proton nuclear magnetic resonance: chemical shifts at 6.25 ppm (m,1H), 6.25 ppm (m,O,5H), 6.05 ppm (m,O,5H), 5.45 to 4.1 (m,2H+10M), 3.75ppm (s,3H) and 2.3 to 0.8 ppm (m,6H).

Example 39

0.2 mol of glutaraldehyde (obtained by distillation from 50% aqueousglutaraldehyde) and 1 mol of methyl acrylate, 0.1 mol ofdiazabicyclo[2.2.2]octane are introduced successively into a glass roundbottom flask of 3 l capacity. The mixture is stirred at 25° C. for 72hours and is then treated as in Examples 1 to 25. The isolated yield ofproduct: ##STR22## is 85%.

Example 40

0.2 mol of thiophene-2,5-dicarboxaldehyde, 0.4 mol of methyl acrylate,0.2 mol of diazabicyclo[2.2.2]octane and 50 ml of dichloromethane areintroduced successively into a glass round bottom flask of 3 l capacity.The mixture is stirred at 25° C. for 105 minutes and is then treated asin Examples 1 to 25. Analysis by gas phase chromatography shows theformation, in an isolated yield of 67%, of a compound identified as thatof formula ##STR23## by the following techniques infraredspectrophotometry: the spectrum obtained shows characteristic bands at3462 cm⁻¹, 1718 cm⁻¹, 1670 cm⁻¹ and 1456 cm⁻¹ ;

carbon-13 nuclear magnetic resonance: chemical shifts at 183.3 ppm,165.9 ppm, 157.5 ppm, 142.3 ppm, 140.6 ppm, 136.9 ppm, 126.8 ppm, 125.6ppm, 68.8 ppm and 52.0 ppm;

proton nuclear magnetic resonance: chemical shifts at 9.8 ppm (s,1H),7.6 ppm (d, 1H), 7.1 ppm (d, 1H), 6.4 ppm (m, 1H), 6.1 ppm (m, 1H), 5.8ppm (m, 1H), 4.2 ppm (m, 1H,OH) and 3.7 ppm (s,3H).

Example 41

0.2 mol of thiophene-2,5-dicarboxaldehyde, 2 mol of methyl acrylate and0.2 mol of diazabicyclo[2.2.2]octane are introduced successively into aglass round bottom flask of 3 l capacity. The mixture is stirred at 25°C. for 46 hours and is then treated as in Examples 1 to 25. Analysis bygas phase chromatography shows the formation, in an isolated yield of67%, of the diacrylate of formula: ##STR24##

The latter was identified by:

infrafred spectrophotometry: the spectrum obtained shows characteristicbands at 3460 cm⁻¹, 1709 cm⁻¹, 1632 cm⁻¹ and 1439 cm⁻¹ ;

proton nuclear magnetic resonance: chemical shifts at 6.7 ppm (s,2H),6.3 ppm (m,2H), 6.0 ppm (m,2H), 5.7 ppm (m,2H), 3.7 ppm (s,6H) and 3.5ppm (m,2H,OH);

carbon-13 nuclear magnetic resonance: chemical shifts at 166.2 ppm,145.3 ppm, 141.1 ppm, 125.8 ppm, 124.4 ppm, 66.6 ppm and 51.6 ppm.

Example 42

0.2 mol of 4,4'-biformyldiphenyl, 1 mol of methyl acrylate and 0.2 molof diazabicyclo[2.2.2]octane and 150 ml of tetrahydrofuran areintroduced successively into a glass round bottom flask 3 l in capacity.The mixture is stirred at 25° C. for 20 days and is then treated as inExamples 1 to 25. A 56% yield is obtained of the compound identified asthat of formula: ##STR25## by the following techniques: infraredspectroscopy: the spectrum obtained (FIG. 1i) shows characteristic bandsat 3474 cm⁻¹, 1722 cm⁻¹, 1702 cm⁻¹ and 1631 cm⁻¹ ;

proton nuclear magnetic resonance: chemical shifts at 9.9 ppm (s,1H),7.85 to 7.55 ppm (m,8H), 6.37 ppm (m, 1H), 5.95 ppm (m, 1H), 5.65 ppm(m, 1H), 3.7 ppm (s, 3H) and 3.4 ppm (m, 1H,OH);

carbon-13 nuclear magnetic resonance: chemical shifts at 191.8 ppm,166.25 ppm, 146.3 ppm, 141.8 ppm, 138.5 ppm, 134.7 ppm, 129.1 ppm, 127.1ppm, 127.0 ppm, 125.2 ppm, 72.0 ppm and 51.6 ppm.

Example 43

0.2 mol of 4,4'-biformyldiphenyl, 2 mol of methyl acrylate and 0.4 molof diazabicyclo[2.2.2]octane are introduced successively into a glassround bottom flask 3 l in capacity. The mixture is stirred at 25° C. for168 hours and is then treated as in Examples 1 to 25. Analysis by gasphase chromatography shows the formation, in an isolated yield of 86%,of the diacrylate of formula: ##STR26##

The latter was identified by:

infrared spectrophotometry: the spectrum obtained shows characteristicbands at 3466 cm⁻¹, 1724 cm⁻¹, 1702 cm⁻¹, 1629 cm⁻¹, 1494 cm⁻¹ and 1437cm⁻¹ ;

proton nuclear magnetic resonance (FIG. 16): chemical shifts at 7.6 ppm(m,8H), 6.4 ppm (m,2H), 5.9 ppm (m,2H), 5.6 ppm (m,2H) and 3.8 ppm(s,6R);

carbon-13 nuclear magnetic resonance: chemical shifts at 166.5 ppm,141.8 ppm, 140.8 ppm, 126.6 ppm, 125.6 ppm, 72.3 ppm and 51.7 ppm.

Example 44

0.2 mol of furan-2,5-dicarboxaldehyde, 1 mol of methyl acrylate, 0.2tool of diazabicyclo[2.2.2]octane and ml of tetrahydrofuran areintroduced successively into a glass round bottom flask 3 l in capacity.The mixture is stirred at 20° C. for 4 hours and is then treated as inExamples 1 to 25. Analysis by gas phase chromatography shows theformation, in an isolated yield of 50%, of the monoacrylate of formula:##STR27##

The latter was identified by:

infrared spectroscopy: the spectrum obtained (Figure showscharacteristic bands at 3454 cm⁻¹, 1725 cm⁻¹, 1705 cm⁻¹, 1678 cm⁻¹ and1582 cm⁻¹ ;

proton nuclear magnetic resonance: chemical shifts at 9.8 ppm (s, 1H),7.3 ppm (d, 1H,J=4 Hz), 6.6 ppm (d, 1H,J=4 Hz), 6.5 ppm (m, 1H), 6.2 ppm(m, 1H), 5.8 ppm (m, 1H), 4.3 ppm (m, 1H,OH) and 3.8 ppm (s, 3H);

carbon- 13 nuclear magnetic resonance: chemical shifts at 177.7 ppm,165.6 ppm, 161.1 ppm, 151.6 ppm, 139.4 ppm, 127.2 ppm, 109.6 ppm, 65.7ppm and 51.7 ppm.

Example 45

0.2 mol of furan-2,5-dicarboxaldehyde, 2 mol of methyl acrylate and 0.4mol of diazabicyclo[2.2.2 ]octane are introduced successively into aglass round bottom flask 3 l in capacity. The mixture is stirred at 20°C. for 27 hours and is then treated as in Examples 1 to 25. Analysis bygas phase chromatography shows the formation, in an isolated yield of60%, of the diacrylate of formula: ##STR28##

The latter was identified by:

infrared spectroscopy: the spectrum obtained shows characteristic bandsat 3457 cm⁻¹, 1723 cm⁻¹ and 1635 cm⁻¹ ;

proton nuclear magnetic resonance: chemical shifts at 6.4 ppm (m,2H),6.2 ppm (s,2H), 6.0 ppm (m,2H), 5.6 ppm (m,2H), 3.8 ppm (s,6H) and 4-3.5ppm (m,2H,OH);

carbon-13 nuclear magnetic resonance: chemical shifts at 166.0 ppm,153.7 ppm, 139.3 ppm, 126.1 ppm, 107.6 ppm, 65.3 ppm and 51.6 ppm.

Example 46

0.2 mol of 3,3'-biformyldiphenyl, 1 mol of methyl acrylate, 0.2 mol ofdiazabicyclo[2.2.2]octane and 150 ml of tetrahydrofuran are introducedsuccessively into a glass round bottom flask 3 l in capacity. Themixture is stirred at 20° C. for 192 hours and is then treated as inExamples 1 to 25. Analysis by gas phase chromatography shows theformation, in an isolated yield of 56%, of the monoacrylate of formula:##STR29##

The latter was identified by:

infrared spectroscopy: the spectrum obtained shows characteristic bandsat 3489 cm⁻¹, 1724 cm⁻¹, 1704 cm⁻¹, 1631 cm⁻¹, 1602 cm⁻¹, 1581 cm⁻¹,1474 cm⁻¹ and 1441 cm⁻¹ ;

proton nuclear magnetic resonance: chemical shifts at 10.1 ppm (s,1H),8.2 to 7.3 ppm (m,8H), 6.3 ppm (m, 1H), 5.9 ppm (m, 1H), 5.75 to 5.5 ppm(m, 1H), 3.7 ppm (s,3H) and 3.6 to 3.4 ppm (m, 1H,OH);

carbon-13 nuclear magnetic resonance: chemical shifts at 192.2 ppm,166.2 ppm, 142.2 ppm, 141.9 ppm, 141.3 ppm, 139.1 ppm, 136.3 ppm, 132.6ppm, 129.0 ppm, 128.6 ppm, 128.2 ppm, 127.7 ppm, 126.1 ppm, 126.0 ppm,125.4 ppm, 125.1 ppm, 72.1 ppm and 65.3 ppm.

Example 47

0.2 mol of 3,3'-biformyldiphenyl, 2 mol of methyl acrylate and 0.4 molof diazabicyclo[2.2.2]octane are introduced successively into a glassround bottom flask 3 l in capacity. The mixture is stirred at 20° C. for84 hours and is then treated as in Examples 1 to 25. Analysis by gasphase chromatography shows the formation, in an isolated yield of 94%,of the diacrylate of formula: ##STR30##

The latter was identified by:

infrared spectroscopy: the spectrum obtained shows characteristic bandsat 3471 cm⁻¹, 1724 cm⁻¹, 1632 cm⁻¹, 1604 cm⁻¹, 1583 cm⁻¹, 1475 cm⁻¹ and1440 cm⁻¹ ;

proton nuclear magnetic resonance: chemical shifts at 7.8 to 7.3 ppm(m,8H), 6.4 ppm (m,2H), 5.9 ppm (m,2H), 5.6 ppm (m,2H), 3.7 ppm (s,6H)and 3.5 ppm (m,2H,OH);

carbon-13 nuclear magnetic resonance: chemical shifts at 166.5 ppm,141.9 ppm, 141.8 ppm, 140.8 ppm, 128.6 ppm, 126.4 ppm, 125.8 ppm, 125.5ppm; 125.3 ppm, 72.3 ppm and 51.6 ppm.

Polymers and copolymers can be made from any and all of the monomersproduced in the above examples.

The preceding examples can be repeated with similar success bysubstituting the generically or specifically described reactants and/oroperating conditions of this invention for those used in the precedingexamples.

From the foregoing description, one skilled in the art can easilyascertain the essential characteristics of this invention, and withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various usages andconditions.

We claim:
 1. Process for the preparation of the acrylates chosen fromthose of formula ##STR31## those of formula ##STR32## and those offormula ##STR33## in which: R is a radical chosen from alkyl radicalscontaining from 1 to 12 carbon atoms, cycloalkyl radicals containingfrom 5 to 12 carbon atoms, and aryl, arylalkyl and alkylaryl radicals,Yis a radical chosen from alkylene radicals containing from 1 to 12carbon atoms, arylene radicals containing from 6 to 12 carbon atoms,heterocyclic radicals whose ring contains from 5 to 10 members and whoseheteroatom is chosen from nitrogen, oxygen and sulphur, and alkylaryleneradicals in which the alkyl part contains from 1 to 4 carbon atoms, andY not being able to denote 1,4-phenylene when R denotes methyl, Z is ahydrocarbon radical containing at least two carbon atoms forming withthe oxygen and the two adjacent carbons a ring containing 4 to 8members,characterized in that an acrylate of formula ##STR34## isreacted with a dialdehyde of formula ##STR35## in the presence of aneffective quantity of at least one functionalization catalyst, whereinselectivity of the reaction toward the production of monoacrylates offormulae I and III or diacrylates of formula II is controlled byadjusting one or more of the parameters selected from the groupconsisting of: the duration of the reaction, the solvent employed, thequantity of solvent employed, the functionalization catalyst employed,the quantity of functionalization catalyst employed, theacrylate/dialdehyde molar ratio, the reaction temperature, the reactionpressure, the electrophilic activator employed, and the amount ofelectrophilic activator employed.
 2. Process according to claim 1,characterised in that the functionalization catalyst is a cyclictertiary amine containing at least one nitrogen atom common to threerings.
 3. Process according to claim 1, characterised in that thefunctionalisation catalyst is employed in a proportion of 2 to 20 mol %relative to the sum of the acrylate and dialdehyde.
 4. Process accordingto claim 1, characterised in that it is carried out in the presence ofat least one electrophilic activator.
 5. Process according to claim 1,characterised in that it is carried out in the presence of an organicsolvent.
 6. Process according to claim 1, characterised in that it iscarried out at a temperature of between 15° C. and 125° C..
 7. Processaccording to claim 1, characterised in that the acrylate/dialdehydemolar ratio is between 0.2 and
 10. 8. Process according to claim 2,characterised in that the functionalisation catalyst is employed in aproportion of 2 to 20 mol % relative to the sum of the acrylate anddialdehyde.
 9. Process according to claim 2, characterised in that it iscarried out in the presence of at least one electrophilic activator. 10.Process according to claim 6, characterised in that it is carried out inthe presence of at least one electrophilic activator.
 11. Processaccording to claim 2, characterised in that it is carried out at atemperature of between 15° C. and 125° C.
 12. Process according to claim4, characterised in that it is carried out at a temperature of between15° C. and 125° C.
 13. Process according to claim 2, characterised inthat the acrylate/dialdehyde molar ratio is between 0.2 and
 10. 14.Process according to claim 4, characterised in that theacrylate/dialdehyde molar ratio is between 0.2 and
 10. 15. Processaccording to claim 6, characterised in that the acrylate/dialdehydemolar ratio is between 0.2 and
 10. 16. Process according to claim 12,characterised in that the acrylate/dialdehyde molar ratio is between 0.2and
 10. 17. A method as in claim 1, wherein the reaction selectivity iscontrolled to provide a product ratio of monoacrylates of formulae I andIII to the diacrylates of formula II within the range of 100:0 to 2:98.18. A method as in claim 2, wherein the reaction selectivity iscontrolled to provide a product ratio of monoacrylates of formulae I andIII to the diacrylates of formula II within the range of 100:0 to 2:98.19. A method as in claim 3, wherein the reaction selectivity iscontrolled to provide a product ratio of monoacrylates of formulae I andIII to the diacrylates of formula II within the range of 100:0 to 2:98.20. A method as in claim 5, wherein the organic solvent is selected fromtetrahydrofuran, methylene chloride, chloroform, dioxice, acetonitrile,methylethylketone, ethanol and ethylacetate.
 21. A method as in claim 5,wherein the amount of solvent ranges from about 20-164 ml per mole ofacrylate.
 22. A method as in claim 10, wherein the reaction is carriedout in the presence of an organic solvent in an amount from about 20-164ml per mole of acrylate.
 23. A method as in claim 1, wherein selectivityof the reaction toward the production of monoacrylates of formula I orIII ranges from 80-100%.
 24. A method as in claim 1, wherein theselectivity of the reaction toward the production of diacrylates offormula II ranges from 70-96%.
 25. A method as in claim 23, wherein thereaction time ranges from 0.8 to 24 hours.
 26. A method as in claim 24,wherein the reaction time ranges from about 24-96 hours.
 27. A method asin claim 1 which is performed in two stages wherein the monoacrylates offormula I are prepared in the first stage and the monoacrylate offormula I formed is converted to a diacrylate of formula II in thesecond stage, wherein one or more of the following reaction parametersof the first stage the second stage are different: the solvent employed,the quantity of solvent employed, the functionalization catalystemployed, the quantity of functionalization catalyst employed, and thereaction temperature.
 28. A method as in claim 27, wherein the yield ofmonoacrylates of formula I produced in the first stage ranges from80-100% and the yield of diacrylates of formula II produced in thesecond stage ranges from 70-96%.
 29. A process as in claim 1, whereinthe proportion of monoacrylates and diacrylates produced is controlledby manipulation of the reaction time.
 30. A process as in claim 21,wherein the selectivity of the reaction toward the production ofmonoacrylates of formulae I and III is increased by limiting theduration of the reaction to less than 3 hours.
 31. A method as in claim21, wherein the selectivity of the reaction toward the production ofdiacrylates of formulae II increased by extending the duration of thereaction more than 3 hours.
 32. A method as in claim 1, wherein theproportion of monoacrylates and diacrylates produced is controlled bythe selection of solvent.
 33. A method as in claim 32, wherein theselectivity of the reaction toward the production of diacrylates offormula II is increased by the use of tetrahydrofuran and/or methylenechloride solvent.
 34. A method as in claim 1, wherein the proportion ofmonoacrylates and diacrylates is controlled by the selection of themolar ratio of acrylates/dialdehyde.
 35. A method as in claim 34,wherein selectivity of the reaction toward the production of diacrylatesof formula II is increased by increasing the molar ratio ofacrylates/dialdehyde.